Chlorosulphonyl vinyl isocyanates and a process for their production

ABSTRACT

Chlorosulphonyl vinyl isocyanates are produced by reacting either an Alpha -halogenated isocyanide dichloride or an Alpha , Beta -unsaturated isocyanide dichloride with a halogen sulphonic acid. The chlorosulphonyl vinyl isocyanates produced are useful in the preparation of plant protection agents, dyestuffs and detergents and as monomers for the production of plastics.

United States Patent [1 1 3,674,829 Arlt July 4, 1072 [54]CHLOROSULPHONYL VINYL [56] References Cited ISOCYANATES AND A PROCESSFOR THEIR UNITED STATES PATENTS 2,675,371 4/1954 COOVGX et al..260/465.9 X [72] Invent Germany 2,514,328 7/1950 Jones ..260/453 x[73] Assignee: Farbenfabriken Bayer Aktiengesellschaft, 3,437,680 4/1969 Farrissey et al ..260/453 Leverkusen, Germany FOREIGN PATENTS ORAPPLICATIONS [22] Flled: June 3,1969 F182 7 4 1956 G 260 453 7 21 Appl,No.: 830,113 many Primary Examiner-Floyd D. Higel [30] Fo i n A li tionPrio it D t Att0meyRobert A. Gerlach and George W. Rauchfuss, Jr.

June 6, 1968 Germany ..P 17 68 608.7 [57] ABSTRACT [52] [1.8. CI.260/453 AL,7l/98,252/545, Chlorosulphonyl vinyl isocyanates are producedby reacting 260/80 R, 260/ 144, 260/243 R, 260/453 AR, either ana-halogenated isocyanide dichloride or an a, B-un- 260/453 260/456260/513 260/513 saturated isocyanide dichloride with a halogen sulphonicacid. 260/543 6 D The chlorosulphony] vinyl isocyanates produced areuseful in [Sl] Int. Cl ---C C070 143/70 the preparation of plantprotection agents, dyestuffs and de- FieId Search AR, 453 AL, 453tergents and as monomers for the production of plastics.

6 Claims, No Drawings CHLOROSULPHONYL VINYL ISOCYANATES AND A PROCESSFOR THEIR PRODUCTION This invention relates to chlorosulphonyl vinylisocyanates. More particularly, this invention relates tochlorosulphonyl vinyl isocyanates and to a process for the production ofchlorosulphonyl vinyl isocyanates.

A wide variety of processes are known for the production of organicisocyanates. The process in most general use, however, is that ofphosgenation of primary amines. The use of phosgene, however, ishazardous and phosgene is poisonous. In addition, however, other methodsnot requiring phosgene are known for the preparation of organicisocyanates including, for example, the Curtius rearrangement of acidazides as well as the Hofmann and Lossen rearrangements. Moreover, it isknown to thermally decompose carbamates and ureas to form thecorresponding isocyanate. Still another method of preparing isocyanatewhile avoiding the use of phosgene is to react an N,N'-disubstituted ortrisubstituted urea with a relatively high boiling isocyanate. Thelatter process results in the isocyanate separating out and leaving theorganic radical of the starting material on the urea. This process,however, suffers from the disadvantage that the ureas are not verysoluble in the isocyanates so that large excesses of the isocyanateinitially employed are required. It is desirable to have a process forthe production of isocyanates which avoids the use of phosgene becausesome of the amines have other phosgene sensitive groups in the molecule.Furthermore not all isocyanates are obtainable by the phosgenation ofamines. It is also desirable to have a process for the production ofisocyanates yielding relatively high yields of isocyanates in additionto avoiding the use ofphosgene.

It is, therefore, an object of this invention to provide chlorosulphonylvinyl isocyanates and a process for their preparation. A further objectof this invention is to provide a process for the preparation ofchlorosulphonyl vinyl isocyanates which avoids the use of phosgene. Afurther additional object of this invention is to provide a process forthe preparation of chlorosulphonyl vinyl isocyanates in good yields. Astill further object of this invention is to provide a process for thepreparation of chlorosulphonyl vinyl iso cyanates from isocyanidedichloride reactants. Another still further object of this invention isto provide chlorosulphonyl vinyl isocyanates and a process for theproduction thereof, which chlorosulphonyl vinyl isocyanates find use inthe production of plant protecting agents, dyestuffs, detergents and asmonomers for plastics.

The foregoing objects and others which become apparent from thefollowing description are accomplished in accordance with thisinvention, generally speaking, by providing a process for the productionof chlorosulphonyl vinyl isocyanates wherein a halogen sulphonic acid isreacted with an a-halogenated isocyanide dichloride or ana,/3-unsaturated isocyanide dichloride. More particularly, the objectsof this invention are accomplished by preparing chlorosulphonyl vinylisocyanates by reacting a halogen sulphonic acid with an ahalogenatedisocyanide dichloride or an afl-unsaturated isocyanide dichloride at atemperature of from about C. to about 150 C.

The new chlorosulphonyl vinyl isocyanates of this invention are preparedby a novel, chemically unique process which comprises reacting a halogensulphonic acid with an ahalogenated isocyanide dichloride or ana,B-unsaturated isocyanide dichloride, the reaction proceeding inaccordance with the following reaction sequence exemplified with the usewherein R, R X and Y have the meanings defined hereinafter.

The process of this invention is suitable for the preparation of anychlorosulphonyl vinyl isocyanate of the formula clo s N0 0 (I) by thereaction of a halogen sulphonic acid having the formula YSO H with anisocyanide dichloride compound having the formula Y is a halogen atom, Xis a halogen atom, preferably chlorine, and R and R are the same ordifferent and each represents a hydrogen atom, a halogen atom or analkyl radical having from one to 20 carbon atoms, an aryl radical havingfrom six to 20 carbon atoms, an alkenyl radical having from two to sixcarbon atoms, an aralkyl radical having from seven to 12 carbon atoms orsaid radicals substituted with any suitable substituent which isnonreactive with an isocyanato group or with a halogen sulphonic acidsuch as, for example, substituents, such as halogen, nitro, alkyl offrom one to four carbon atoms, alkyl sulphonyl wherein the alkyl radicalcontains one to four carbon atoms, aryl sulphonyl wherein the arylradical contains six to nine carbon atoms, alkyl carbonyl wherein thealkyl radical contains one to four carbon atoms, aryl carbonyl whereinthe aryl radical contains from six to nine carbon atoms, chlorosulphonylor chlorocarbonyl, or R and R taken together may form an alicyclic ring.Most preferably, however, R and R may be the same or different and eachpreferably is a hydrogen atom, a halogen atom, an alkyl radicalcontaining from one to four carbon atoms, an aryl radical containingfrom six to nine carbon atoms or a halogen substituted alkyl radicalcontaining from one to four carbon atoms. The halogen atom may be anysuitable halogen atom such as fluorine, chlorine, bromine or iodine butis preferably chlorine or fluorine. Although R and R may be any of thesuitable radicals set forth above, the following may be mentioned asexamples of suitable R and R radicals: a hydrogen atom, a halogen atom,preferably chlorine or fluorine, an alkyl radical such as, for example,methyl, ethyl, propyl, butyl, nonyl, dodecyl, octadecyl and eicosyl andthe like, aryl radicals such as, for example, phenyl, naphthyl, anthryl,tolyl and the like, aralkyl such as, for example, benzyl, phenylethyland the like, alkenyl such as, for example, propenyl, butenyl, hexenyland the like or said radicals substituted with lower alkyl, halo, nitro,alkoxy, alkyl sulphonyl, aryl sulphonyl, aryl carbonyl, chlorosulphonylor chlorocarbonyl substituents. Although X and Y may be any suitablehalogen atoms such as fluorine, chlorine, bromine or iodine, they arepreferably chlorine atoms.

Although chlorosulphonyl vinyl isocyanates of formula (1) can beobtained from any corresponding a-halogenated isocyanide dichloride ofthe formula wherein R and R and X are as defined above, ora,,B-unsaturated isocyanide dichloride of the formula wherein R and Rare as defined above, the following may be mentioned as examples ofsuitable isocyanide dichloride reactants that may be used in the processaccording to this invention: l-chloroethyl isocyanide dichloride,1,2-dichloroethyl isocyanide dichloride, 1 ,l ,2-trichloroethylisocyanide dichloride, l-chlorol -ch1oromethylpropyl isocyanidedichloride, 2-chlorovinyl isocyanide dichloride, 1,2-

dichlorovinyl isocyanide dichloride, l-methyl-2-chlorovinyl isocyanidedichloride, and styryl isocyanide dichloride.

As examples of suitable halogen sulphonic acid reactants employed in theprocess of this invention there may be mentioned chlorosulphonic acid,fluorosulphonic acid, bromosulphonic acid and iodosulphonic acid.However, the process of this invention is preferably carried oututilizing chlorosulphonic acid or fluorosulphonic acid.

The process of this invention is suitable for the preparation of anychlorosulphonyl vinyl isocyanate of the formula (I) set forthhereinabove. As examples of the chlorosulphonyl vinyl isocyanates thatmay be prepared according to the process of this invention there may bementioned the following:

chlorosulphonyl vinyl isocyanate,

2-methyl-2-chlorosulphonyl vinyl isocyanate, 2-phenyl-2-chlorosulphonylvinyl isocyanate, 2-ethylphenyl-2-chlorosulphonyl vinyl isocyanate,2-chloromethyl-2-chlorosulphonyl vinyl isocyanate,2-nitrophenyl-2-chlorosulphonyl vinyl isocyanate,

2-( methoxyphenyl)-2-chlorosulphonyl vinyl isocyanate,

2-(methylsulphonylphenyl)-2-chlorosulphonyl vinyl isocyanate,2-(phenylsulphonylphenyl)-2-chlorosulphonyl vinyl isocyanate,

2-(acetylphenyl)-2-chlorosulphonyl vinyl isocyanate,

2-( benzoylphenyl )-2-chlorosulphonyl vinyl isocyanate,

2,2-di(chlorosulphonyl) vinyl isocyanate,

2-chloroacetyl-2-chlorosulphonyl vinyl isocyanate,2-butenyl-2-chlorosulphonyl vinyl isocyanate,2-(phenylethyl)-2-chlor0sulphonyl vinyl isocyanate,2-chloro-2-chlorosulphony] vinyl isocyanate, and2-chlorosuIphonyl-cyclohcxcn-I-yl isocyanate.

The process of this invention may be carried out over a wide temperaturerange of generally from about C. to about 150 C., preferably at atemperature of from about 40 C. to about 90 C. The chlorosulphonyl vinylisocyanate product may be separated from the reaction mixture by anysuitable known separation procedure such as, for example, bydistillation, preferably in vacuo.

Generally, the process of this invention is carried out employing amolar ratio of the reactants of from about 0.111 to about 1.221 (halogensulphonic acid isocyanide dichloride). The preferred molar ratio of thereactants is a molar ratio of about 1:1. The reaction may be carried outin the absence of or in the presence of any suitable inert organicdiluent. When an organic diluent is employed, one may use, for example,chlorinated hydrocarbons, such as, chlorobenzene, methylene dichloride,tetrachloroethylene, trichloroethane and the like.

The chlorosulphonyl vinyl isocyanates prepared according to the processof this invention are useful for the production of plant protectionagents, dyestuffs and detergents and are valuable comonomers, forexample, for the production of plastics.

The invention is further illustrated but is not intended to be limitedby the following examples in which all parts and percentages are byweight unless otherwise specified.

EXAMPLE 1 About 985 parts of chlorosulphonic acid are added dropwise atabout 60 C. to about 1650 parts of 1,2-dichloroethyl isocyanidedichloride in such a way that a temperature of from about 60 C. to about70 C. is maintained in the reaction mixture. Hydrogen chloride is givenoff during the reaction. On completion of the reaction, the reactionproduct is distilled in vacuo, giving about 1,490 parts of2-chlorosulphonyl-2- chlorovinyl isocyanate boiling at 103 to 1 10 C./ l2 Torr.

EXAMPLE 2 About 232 parts of chlorosulphonic acid are added dropwise atabout 30 C. to about 40 C. to about 460 parts of 1,1,2-trich1oroethy1isocyanide dichloride. When no more hydrogen chloride is given off, thereaction product is distilled in vacuo giving about 340 parts of2-chlorosulphonyl dichlorovinyl isocyanate boiling at 109-l 15 C. /13Torr.

EXAMPLE 3 About 116 parts of chlorosulphonic acid are added dropwisewith stirring and cooling at about 50 C. to about 116 parts ofchlorovinyl isocyanide dichloride. When no more hydrogen chloride isgiven off, the reaction product is distilled in vacuo giving about partsof chlorosulphonyl chlorovinyl isocyanate boiling at lO7-1 12 C. /l4Torr.

EXAMPLE 4 Preparation of a detergent from chlorosulphonyl chlorovinylisocyanate A solution of 54 g of tetradecanol-( l) in methylene chlorideis added dropwise to a cooled and stirred solution of 51 g ofchlorosulphonyl chlorovinyl isocyanate in 250 ml of methylene chloride.After the addition the solvent is distilled off. The remaining urethanechlorovinyl sulphochloride is hydrolized with a 10 percent solution ofNaOH at room temperature to the corresponding sulphonate. The sodiumsulphonate thus obtained can be used as detergent.

It is to be understood that any of the components and conditionsmentioned as suitable herein can be substituted for its counterpart inthe foregoing examples and that although the invention has beendescribed in considerable detail in the foregoing, such detail is solelyfor the purpose of illustration. Variations can be made in the inventionby those skilled in the art without departing from the spirit and scopeof the invention.

What is claimed is:

l. A chlorosulphonyl vinyl isocyanate having the formula wherein R and Rare hydrogen, halogen or substituted or unsubstituted radicals selectedfrom the group consisting of alkyl having from one to 20 carbon atoms,aryl having from six to 20 carbon atoms, alkenyl having from seven to 12carbon atoms and wherein the substituents on said substituted radicalsare substituents which are nonreactive with isocyanato groups or withhalogen sulphonic acids, the substituents being selected from the groupconsisting of halogen, nitro, alkyl of from one to four carbon atoms,alkyl sulphonyl wherein the alkyl radical contains one to four carbonatoms, aryl sulphonyl wherein the aryl radical contains six to ninecarbon atoms, alkyl carbonyl wherein the alkyl radical contains one tofour carbon atoms, aryl carbonyl wherein the aryl radical contains sixto nine carbon atoms, chlorosulphonyl or chlorocarbonyl.

2. The isocyanate of claim 1 wherein R is hydrogen and R is chlorine.

3. The isocyanate of claim ll wherein R and R are both chlorine.

4. A process for the preparation of a chlorosulphonyl vinyl isocyanateof claim 1 which comprises reacting at a temperature of from about 0 C.to about 150 C. a halogen sulphonic acid having the formula YSO H withan isocyanide dichloride selected from the group consisting of ana-halogenated isocyanide dichloride of the formula or an afi-unsaturatedisocyanide dichloride of the formula

2. The isocyanate of claim 1 wherein R is hydrogen and R1 is chlorine.3. The isocyanate of claim 1 wherein R and R1 are both chlorine.
 4. Aprocess for the preparation of a chlorosulphonyl vinyl isocyanate ofclaim 1 which comprises reacting at a temperature of from about 0* C. toabout 150* C. a halogen sulphonic acid having the formula YSO3H with anisocyanide dichloride selected from the group consisting of an Alpha-halogenated isocyanide dichloride of the formula or an Alpha , Beta-unsaturated isocyanide dichloride of the formula wherein Y and X arehalogen and R1 and R2 are as defined in claim 1, such that the molarratio of halogen sulphonic acid to isocyanide dichloride is from about0.1:1 to about 1.2:1.
 5. The process of claim 4 wherein the reaction isconducted at a temperature of from about 40* C. to about 90* C.
 6. Theprocess of claim 4 wherein the molar ratio of halogen sulphonic acid toisocyanide dichloride is about 1:1.